Products obtained by reacting phosphorus pentasulfide with sulfurized ketones



Patented Jan. 11, 1949 PRQEDUCTSOBTAINEI) BYLREAGTING..PHOSF PHQRUS PENTASULFIDE"; WITH: SULFUR-J IZED KETONES Ferdinand "Pi tto,"W0odhury-, N J and ltonald' E. Meyer; Cumberland, Md, assignors to so cony-Vac-ai1n1 Oil i Company-, Incorporated; at. corporation: ofiNew'York N0 Drawing Application July 25, 1945', SrialNo. 60?;090

This invention has to do with new reaction products which may be: generaliy'designatedlas phosphorua and sulfur-containing reaction prode ucts-obtained- I by reaction: of an unsaturated .:l 'e tone, phosphorus pentasulfide and elementary.

sulfur;

The present inventionis .1 predicatedupon'ithe discovery that the reaction products contemplated: herein when blended with a-viscousniineral oil? fraction such as a hydrocarbon lubricating 'oil Will improvevarious properties of tlieoil. Foi' example, these reaction products will inhibit; oxidation =of' the oil, thereby :retarding the formation of sludge and acidic products. They; also. retard changes inviscosity in the 011, with-term perature change during use;

It' is to be understood; however, that the present invention is not: concerned with mineral oil corn-.- positions; such compositions forming the subject matter ofcur copending application; SGT -SA NQ 49%,868') filed July 8, 1943;- now-t Patent Not 2,383,497, oiwhich the -present application is a continuation-impart and to which reference is made for further detailsin the composition- 0f these reaction products.

It'is to be understood-that the use of the reaction products of this invention is not=confinecito the improvement of mineral. oil fractions. way of illustration they may-beused'as cutting oils, rubber accelerators, extreme-pressure lubri---- cants and as intermediates in the production of other chemical compositions;- Numercus other uses and applications ofthesereaction-products- Will be readily apparent to those skilled-in the art from the description of their composition and typical methods for preparing them, as provided I hereinafter:

The phosphorus and sulfur-containing --reaction'products are stable, non-corrosive and are obtained by: reacting substantially one mol ofphosphorus pentasulfide' with four mols ofa -sul furized ketone at atempera'ture aboveaboutlfii) 0.. and: below the decomposition temperature: oi the reactioniproductathe sulfurized ketone-having been obtained :bysuliurizing an unsaturated ketone with elementary sulfur at a temperature above about.150'C. and below the decomposition temperature of the said sulfurized ketone.

While all. unsaturated ketones may be usedherein, typical of which are didecenyl ketone; phorone, particularly preferred isv dioleyla ketone which :is. alsoknown'in the art as diheptadecenyl ketone. Contemplatedioruse also. .isa technical;

as oleone.

5 Claims. (01. 266-) We have found that the character oi-the reac-' tion: products of this invention is influenced to a large degree-by the reaction temperature in the P285 reaction. l o'rexample, when the reaction of P285 anddioleylketone, or: of P285 and the afore said sulfurized dioleyl ketone; iscarried out at atemperature in'theneighborhoodof 140- Ci, the reaction-product has a relatively high =-neutraliza-- tion number =(N. Ni),-whichisa-measure of its acidity; whereas, when the reaction temperature is maintainedat about 200 CJ, the neutralization number oithe reaction product" is -much lower. Iii other Words; a relatively high temperature 01? the order 0f2U0 C. or-more may be resortedto in order to obtain slightly acidic; or evenneutraL-i reaction products! I The phosphorus and suli1lrcontent ofthe reaction productsoiPzSi and "dic leyl ketonean-d similarly of the reaction-products of 'PiSs' and theaforesaid sulfurized ketone, obtained by varying the' reaction temperature-=--is not soeflcted inasmuch assuch reaction productscontain phosphor-us and sulfur chemically combined at substantially the- P'z'Sa-- Although .the exact chemical structure of the reaction-products of this invention is now known at this time,- our investigations have indicated that-elementary sulfur most probablyreacts at the olefin bonds *of an unsaturated ketone and correspondinglyat'theolefin'bonds of the unsat urated ketone ffis reaction products; andhave This is indicatedzvbyrr the substantial absence of an evolution. of. hydrogen sulfide during the reaction with elementary sulfur andduring the reaction with PSL It" is also borne out by the fact thatr aimostas muchP'z'Ss combines chemically with the 1 sulfurized ketone (unsaturated) aszvwith. unsulfurized unsaturatedketones;

The reaction products of this invention are believedetoxbe novel in. that previous" disclosures have-shown thatscompounds. containing. sulfur,- not. phosphorus ian-dx'suliur, are formed in :there action .of Pzss with'certain ketones. More'speciiically; Springoin theBulhSo'c-n.Chimt (France); 2, v

40; 657;; has J disclosed l' that i a dimer thioket'one;

CGHmS'aiS obtained. when. acetone isWarmed' with P285; and s:Gatterman, .in :th'es Ber; 28,-. 28577, has discl0sed;that.thiobenzop-hen'oneis obtained when benzoph'enone .invbenzene solution is heated with PzSs for several hours-at Ch in abomb.

Thecsu'lfurized ketones-whiohare reacted with 'PzSa to form reaction products contempla'ted same molar ratio as in 3 herein are obtained by heating an unsaturated ketone with elementary sulfur at an elevated temperature, particularly at a temperature above about 150 C. Preferred of such sulfurized ketones are those obtained by treating an unsaturated ketone with from about 5 to about parts of elementary sulfur at a temperature from about 175 C. to about 200 C. The sulfurized ketones so obtained are stable and non-corrosive, and are then reacted with P285. While the reaction with P255 and certain sulfurized ketones may be carried'out at temperatures above about 100 C., it is preferred that the reaction temperatures used fall within the temperature range of 140 C. to 200 C. In this reaction the molar ratio of suliurized ketones to P285 is 4:1. This reaction is carried out for a sufiicient time in order that the reaction product so obtained with be non-corrosive to a polished copper strip immersed in a 1 per cent blend of the reaction product in mineral oil for 3 hours at 150 C.

Similarly, an unsaturated ketone may be reacted with P285 in a molar ratio of 4:1 at the aforesaid reaction temperatures above about 100 C. and. the phosphorusand sulfur-containing reaction products so obtained may then be reacted with elementary sulfur at an elevated temperature. In this regard, the amount of elementary sulfur used and the reaction temperature em ployed will be as indicated above.

Several modifications of the procedure described above may be resorted to for the obtainment of particularly desirable products. We have found that the use of a nonoxidizing or inert gas, such that the reaction mixture is under a 3 non-oxidizing atmosphere, provides us with reaction products characterized by a high degree of stability. Inert gases, such as nitrogen, carbon dioxide, etc., may be used for this purpose in both the Pass reaction and in the sulfurizing reaction. As another modification unreactive or substantially inert diluents such as acid treated kerosene may be used during these reactions, or maybe admixed with the reaction products so obtained to aid in refining the same, and may be removed thereafter by a suitable means such as by distillation. For example, a mineral oil may be used as an inert diluent in order to obtain a mineral oil blend or concentrate of the desired reaction product.

The reaction products contemplated herein and the preparation thereof are illustrated by the following typical examples in which a particularly preferred ketone, oleone, is used:

EXAMPLE 1 Reaction product of sulfurz'zed oleone and P285 in mineral oil (a) Preparation of sulfurized oleone:

Seventy-five grams of oleone, 8.5 grams of elementary sulfur and 150 grams of mineral oil diluent (Saybolt Universal Viscosity of 67 seconds at 210 F.) are charged to a reaction vessel equipped with a mechanically-driven stirrer, an upright Liebig condenser, a thermometer and an inlet tube extending to within a few inches above the mixture. The atmosphere above the mixture is constantly swept with nitrogen gas (introduced through the aforesaid inlet tube) in order to maintain a non-oxidizing atmosphere above the mixture. The mixture is stirred and heated at 170 C. for 3 hours and the reaction product so obtained is sulfurized oleone.

(1)) Preparation of sulfurized oleone-P285 reaction product:

The reaction product obtained in (a) is allowed to cool to C. and 9.0 grams of P235 are then added. The reaction mixture is stirred and heated at 140 C. for 2 hours and is then filtered through Hi-Flo on a steam heated Buchner funnel in order to remove any deleterious by-products and any unreacted P2S5. The reaction product is a brown viscous oil containing 5.1 per cent sulfur and 0.67 per cent phosphorus and has a neutralization number (N. N.) of 14.5

A three per cent blend of this sulfurized oleone-P285 reaction product obtained in mineral oil, that is, a 1 per cent blend of this concentrate in mineral .oil, caused only a slight tarnish or discoloration of a polished copper strip immersed in said blend for 3 hours at C.

EXAMPLE 2 Reaction product of oleone-P285 and s lfur in mineral oil (a) Preparation of oleone-P285 reaction product:

Sixty-five grams of mineral oil diluent (Saybolt Universal viscosity of 67 seconds at 210 F.), 60 grams of oleone and 6.6 grams of P285 were charged to a vessel equipped as described in Example 1 (a), and were stirred and heated at 200 C. for 2%; hours. The reaction mixture was then filtered through Hi-Flo on a steam heated Buchner funnel in order to remove any deleteri- 011s icy-products and any unreacted P285.

(b) Preparation of oleone-P255 and sulfur reaction products:

One hundred and thirty grams of the oleone- PzSs reaction product obtained in (a), that is, a 1:1 blend of the product in mineral oil, was heated with 6 grams of elementary sulfur at C. for 2 hours. As the reaction product thus obtained was gelatinous, 130 grams of mineral oil were added thereto in order to obtain a fluid mixture. The final product, a 1:3 blend in mineral oil, analyzed as follows: 0.51 per cent phosphorus, 3.94 per cent sulfur and 2.9 neutralization number.

It is to be understood that although we have described certain typical procedures for preparing the reaction products contemplated herein and have shown illustrative reaction products, the invention is not limited to the particular procedures or products, but includes within its scope such changes and modifications as fairly come within the spirit of the appended claims.

We claim:

1. As a new composition of matter, a phosphorusand sulfur-containing reaction product obtained by reacting substantially one mol of phosphorus pentasulfide with four mols of a sulfurized ketone at a temperature between about 100 C. and about 200 C., said sulfurized ketone being obtained by sulfurizing an unsaturated acyclic ketone containing no substituents other than hydrogen, with elementary sulfur at a temperature above about 150 C. and below the decomposition temperature of said sulfurized ketone.

2. As a new composition of matter, a phosphorusand sulfur-containing reaction product obtained by reacting substantially one mol of phosphorus pentasulfide with four mols of a sulfurized ketone at a temperature between about 100 C. and about 200 0., said sulfurized ketone being obtained by sulfurizing an unsaturated acyclic ketone containing no substituents other than hydrogen, with elementary sulfur at a tem-.

perature between about 150 C. and about 200 C.

3. As a new composition of matter, a phosphorusand sulfur-containing reaction product obtained by reacting substantially one mol of phosphorus pentasulfide with four mols of a sulfurized ketone at a temperature between about 100 C. and about 200 C., said sulfurized ketone being obtained by sulfurizing an unsaturated acylic ketone containing no substituents other than hydrogen, with from about 5 per cent to about per cent by weight of elementary sulfur at a temperature aboveabout 150 C. and below the decomposition temperature of said sulfurized ketone. :5

4 As a new compo tion of matter, a. phosphorusand sulfur-containing reaction product obtained by reacting fubstantially one mol of phosphorus pentasul I. e with four mols of a sulfurized dioleyi ketojne at a temperature between about C. and about 200 0., said sul iurlzed dioleyl ketone being obtained by sulfurizweight of elementary 0 Number ingjdioleyl ketone with elementary sulfur at a temperature between about C. and about 200v C.

As a new composition of matter, a phosphorusand sulfur-containing reaction product obtained by reacting substantially one moi of phosphorus pentasulfide with four mols of a sulfurized dioleyl ketone at about 140 C., said sulff -urized dioleyl ketone being obtained by sulfurizi z' g dioleyl ketone with about 10 per cent by sulfur at about C. FERDINAND P. OTTO. RONALD E. MEYER.

REFERENCES CITED y The following references are of record in the 'file of this patent:

UNITED STATES PATENTS Name Date Certificate of Correction Patent No. 2,459,090. January 11, 1949. FERDINAND P. OTTO ET AL.

It is hereby certified that errors appear in the printed specification of the above numbered patent requiring correction as follows:

Column 2, line 26, for the word now read not; column 3, line 18, for with read will;

and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Oflice.

Signed and sealed this 31st day of May, A. D. 1949.

THOMAS F. MURPHY,

Assistant G'ommissz'On-er of Patents. 

